9-[(2R,3R,4R,5R)-3,4-Bis-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-6-chloro-2,8-bis-trimethylsilanyl-9H-purine | 171612-98-9

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷
• 英文名称: 9-[(2R,3R,4R,5R)-3,4-Bis-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-6-chloro-2,8-bis-trimethylsilanyl-9H-purine
• 英文别名: [9-[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-6-chloro-2-trimethylsilylpurin-8-yl]-trimethylsilane
• CAS: 171612-98-9
• 化学式: C₃₄H₆₉ClN₄O₄Si₅
• 分子量: 773.827
• InChiKey: IWTNQCYWBFXWDV-CTDWIVFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.27
• 重原子数：
  48
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  80.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  6-chloro-9-(2,3,5-tris-O-(tert-butyldimethylsilyl)-β-D-ribofuranosyl)-9H-purine 、 9-[(2R,3R,4R,5R)-3,4-Bis-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-6-chloro-2,8-bis-trimethylsilanyl-9H-purine 在 六甲基磷酰三胺 、 2,2,6,6-tetramethylpiperidinyl-lithium 作用下， 生成 [9-[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-6-chloropurin-2-yl]-trimethylsilane
  参考文献：
  名称：

  Lithiation-mediated CC silyl and stannyl migrations observed in 6-chloro-9-(β-d-ribofuranosyl)purine

  摘要：

  Lithiation of 9-[2,3,5-tris-O-(tert-butyldimethylsilyl)-beta-D-ribofuranosyl]-6-chloropurine (1) with LTMP (lithium 2,2,6,6-tetramethylpiperidide) and a subsequent reaction with either Me(3)SiCl or Bu(3)SnCl was found to effect C-2-substitution, as a result of ''silyl or stannyl migration'' from C-8 to C-2 position. Transformation of the resulting 2-stannyl derivative (8) to 2-substituted adenosines was also examined briefly.

  DOI：

  10.1016/0040-4039(95)01302-x
• 作为产物：
  描述：

  三甲基氯硅烷 、 6-chloro-9-(2,3,5-tris-O-(tert-butyldimethylsilyl)-β-D-ribofuranosyl)-9H-purine 在 2,2,6,6-tetramethylpiperidinyl-lithium 作用下， 生成 [9-[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-6-chloropurin-2-yl]-trimethylsilane 、 [9-[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-6-chloropurin-8-yl]-trimethylsilane 、 9-[(2R,3R,4R,5R)-3,4-Bis-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-6-chloro-2,8-bis-trimethylsilanyl-9H-purine
  参考文献：
  名称：

  Lithiation-mediated CC silyl and stannyl migrations observed in 6-chloro-9-(β-d-ribofuranosyl)purine

  摘要：

  Lithiation of 9-[2,3,5-tris-O-(tert-butyldimethylsilyl)-beta-D-ribofuranosyl]-6-chloropurine (1) with LTMP (lithium 2,2,6,6-tetramethylpiperidide) and a subsequent reaction with either Me(3)SiCl or Bu(3)SnCl was found to effect C-2-substitution, as a result of ''silyl or stannyl migration'' from C-8 to C-2 position. Transformation of the resulting 2-stannyl derivative (8) to 2-substituted adenosines was also examined briefly.

  DOI：

  10.1016/0040-4039(95)01302-x

文献信息

• A New Entry to 2-Substituted Purine Nucleosides Based on Lithiation-Mediated Stannyl Transfer of 6-Chloropurine Nucleosides
  作者：Keisuke Kato、Hiroyuki Hayakawa、Hiromichi Tanaka、Hiroki Kumamoto、Satoru Shindoh、Satoshi Shuto、Tadashi Miyasaka

  DOI：10.1021/jo970398q

  日期：1997.10.1

  In spite of exclusive lithiation at the 8-position of 9-(2,3,5-tris-O-TBDMS-beta-D-ribofuranosyl)-6-chloropurine (2) with LDA, subsequent quenching of its lithiated species with Bu3SnCl (or TMSCl) results in the formation of 2-substituted products. Under optimized reaction conditions, where LTMP was us ed as a lithiating agent, 9-(2,3,5-tris-O-TBDMS-beta-D-ribofuranosyl)-6-chloro-2-(tributylstannyl)purine (11) was formed in quantitative yield. Several experiments carried out to verify the reaction mechanism suggested that an anionic stannyl (or silyl) transfer from the 8- to the 2-position had been involved. Manipulation of the 2-tributylstannyl group in 11 and in its adenine counterpart (22) has disclosed a new entry to 2-substituted purine nucleosides. This chemistry was briefly applied to the synthesis of the 2-fluoro analogue of neplanocin A.